TWI671525B - Biosensor electrode and biosensor using the same - Google Patents
Biosensor electrode and biosensor using the same Download PDFInfo
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Abstract
本發明涉及一種生物感測器電極，其包括一多孔金屬複合結構，該多孔金屬複合結構包括一多孔金屬結構及一奈米碳管結構，該奈米碳管結構固定在所述多孔金屬結構的表面，所述奈米碳管結構包括多根奈米碳管，所述多孔金屬複合結構包括多個褶皺部。本發明進一步涉及一種生物感測器。The invention relates to a biosensor electrode, which comprises a porous metal composite structure. The porous metal composite structure includes a porous metal structure and a nano carbon tube structure. The nano carbon tube structure is fixed to the porous metal. On the surface of the structure, the nano carbon tube structure includes a plurality of nano carbon tubes, and the porous metal composite structure includes a plurality of folds. The invention further relates to a biosensor.
Description
本發明涉及一種生物感測器電極及生物感測器。The invention relates to a biosensor electrode and a biosensor.
生物感測器用於檢測生物分子的濃度，需要具有靈敏度高，可靠性好，反應迅速，選擇性良好以及成本低的特點。該生物感測器由分子識別元件和訊號轉換元件構成，該分子識別元件識別生化反應訊號，轉換元件用於將生化反應訊號轉換成電訊號。Biosensors are used to detect the concentration of biomolecules. They need to have the characteristics of high sensitivity, good reliability, fast response, good selectivity, and low cost. The biosensor is composed of a molecular recognition element and a signal conversion element, the molecular recognition element recognizes a biochemical reaction signal, and the conversion element is used to convert the biochemical reaction signal into an electric signal.
生物感測器中的分子識別元件一般由電極和具有電催化性能的材料組成，所述具有電催化性能的材料一般通過粘結或物理接觸與所述電極組合，該電極用於收集生化反應產生的電流，所述具有電催化性能的材料與待測的生物分子進行生化反應，用於進行催化。The molecular recognition element in a biosensor is generally composed of an electrode and a material having electrocatalytic performance, and the material having electrocatalytic performance is generally combined with the electrode through bonding or physical contact, and the electrode is used for collecting biochemical reaction generated Current, the material with electrocatalytic performance performs a biochemical reaction with the biomolecule to be tested for catalysis.
先前，一般採用的電極材料為奈米多孔金屬，由於該奈米多孔金屬具 有較大的比表面積，實現更高的靈敏度和更低的檢測限度。但是，如圖1所示，該皺縮的奈米多孔金屬存在韌帶連接不完整的現象，使得該皺縮的奈米多孔金屬機械強度低及韌性差，容易發生斷裂，從而影響生物感測器電極和生物感測器的使用壽命。Previously, nano-porous metal was generally used as the electrode material. Since the nano-porous metal has a large specific surface area, higher sensitivity and lower detection limits are achieved. However, as shown in FIG. 1, the shrunken nanoporous metal has an incomplete ligament connection, so that the shrunken nanoporous metal has low mechanical strength and poor toughness, and is prone to fracture, thereby affecting the biosensor. Electrode and biosensor life.
有鑑於此，確有必要提供一種使用壽命較長的生物感測器電極和生物感測器。In view of this, it is indeed necessary to provide a biosensor electrode and a biosensor with a long service life.
一種生物感測器電極，該電極包括一多孔金屬複合結構，該多孔金屬複合結構包括一多孔金屬結構及一奈米碳管結構，該奈米碳管結構固定在所述多孔金屬結構的表面，所述奈米碳管結構包括多根奈米碳管，所述多孔金屬複合結構包括多個褶皺部。A biosensor electrode, the electrode includes a porous metal composite structure, the porous metal composite structure includes a porous metal structure and a nano carbon tube structure, and the nano carbon tube structure is fixed to the porous metal structure. On the surface, the nano carbon tube structure includes a plurality of nano carbon tubes, and the porous metal composite structure includes a plurality of folds.
一種生物感測器，該生物感測器包括一分子識別元件和一訊號轉換元件，所述分子識別元件用於識別待測生物分子被催化後產生的生化反應訊號，所述訊號轉換元件將所述分子識別元件識別到的生化反應訊號轉換成電化學訊號，所述分子識別元件包括一多孔金屬複合結構，該多孔金屬複合結構包括一多孔金屬結構及一奈米碳管結構，該奈米碳管結構固定在所述多孔金屬結構的表面，所述奈米碳管結構包括多根奈米碳管，所述多孔金屬複合結構包括多個褶皺部。A biosensor includes a molecular recognition element and a signal conversion element. The molecular recognition element is used to identify a biochemical reaction signal generated after the biomolecule to be measured is catalyzed. The biochemical reaction signal recognized by the molecular recognition element is converted into an electrochemical signal. The molecular recognition element includes a porous metal composite structure including a porous metal structure and a nano carbon tube structure. The rice carbon tube structure is fixed on the surface of the porous metal structure, the nano carbon tube structure includes a plurality of nano carbon tubes, and the porous metal composite structure includes a plurality of folds.
與先前技術相比較，本發明提供的生物感測器電極及生物感測器中奈米碳管固定於所述多孔金屬結構的表面，且由於奈米碳管具有良好的機械強度及韌性，所述多孔金屬複合結構不容易斷裂，提高了生物感測器電極及生物感測器的韌性，從而延長了生物感測器電極及生物感測器的使用壽命。Compared with the prior art, the biosensor electrode and the nano-carbon tube provided in the present invention are fixed on the surface of the porous metal structure, and because the nano-carbon tube has good mechanical strength and toughness, The porous metal composite structure is not easy to break, which improves the toughness of the biosensor electrode and the biosensor, thereby extending the service life of the biosensor electrode and the biosensor.
下麵根據說明書圖式並結合具體實施例對本發明的技術方案進一步詳細表述。The technical solution of the present invention will be further described in detail according to the drawings of the specification and specific embodiments.
本發明提供一種生物感測器電極，其包括一多孔金屬複合結構，該多孔金屬複合結構包括一多孔金屬結構及一奈米碳管結構，該奈米碳管結構固定在所述多孔金屬結構的表面，所述奈米碳管結構包括多根奈米碳管，所述多孔金屬複合結構包括多個褶皺部。The invention provides a biosensor electrode, which includes a porous metal composite structure. The porous metal composite structure includes a porous metal structure and a nano carbon tube structure. The nano carbon tube structure is fixed to the porous metal. On the surface of the structure, the nano carbon tube structure includes a plurality of nano carbon tubes, and the porous metal composite structure includes a plurality of folds.
所述生物感測器電極可以僅由多孔金屬複合結構構成，因為一方面所述奈米碳管結構具有良好的機械強度、韌性和導電性，另一方面多孔金屬結構和奈米碳管結構均具有良好的催化性能，所以該多孔金屬複合結構既有導電性又有催化性，可以同時收集電子和進行催化反應。The biosensor electrode may be composed only of a porous metal composite structure, because on the one hand, the nano-carbon tube structure has good mechanical strength, toughness, and electrical conductivity; It has good catalytic performance, so the porous metal composite structure has both electrical conductivity and catalytic properties, and can simultaneously collect electrons and perform catalytic reactions.
請參閱圖2，所述生物感測器電極可以進一步包括催化材料，該催化材料設置於所述多孔金屬複合結構的表面。進一步，所述催化材料位於所述奈米碳管結構中相鄰奈米碳管之間的間隙和多孔金屬結構的韌帶上。所述催化材料與多孔金屬結構一體化，無需引入任何添加劑，降低了電極的內部電阻，提高了生物感測器電極的導電性。Referring to FIG. 2, the biosensor electrode may further include a catalytic material disposed on a surface of the porous metal composite structure. Further, the catalytic material is located on a gap between adjacent nano carbon tubes and a ligament of a porous metal structure in the nano carbon tube structure. The catalytic material is integrated with the porous metal structure without introducing any additives, reducing the internal resistance of the electrode, and improving the conductivity of the biosensor electrode.
該催化材料可以為金屬氧化物、金屬等，能夠進一步提高生物感測器電極的催化性能。所述金屬氧化物可以為Co3 O4 、MnO2 、TiO2 等材料，所述金屬氧化物的形狀可以為奈米顆粒、奈米片、奈米花等。所述電極可以為正極或負極。本實施例中，將多孔金屬複合材料放入含有KMnO4 和水合肼的水溶液中，KMnO4 被還原形成MnO2 顆粒，MnO2 顆粒形成在奈米碳管結構的表面、奈米碳管結構中相鄰奈米碳管之間的間隙及多孔金屬結構的韌帶上。The catalytic material may be a metal oxide, a metal, or the like, which can further improve the catalytic performance of the biosensor electrode. The metal oxide may be materials such as Co 3 O 4 , MnO 2 , TiO 2, and the shape of the metal oxide may be nano particles, nano flakes, nano flowers, and the like. The electrode may be a positive electrode or a negative electrode. In this embodiment, a porous metal composite is placed in an aqueous solution containing KMnO 4 and hydrazine hydrate. KMnO 4 is reduced to form MnO 2 particles, and the MnO 2 particles are formed on the surface of the carbon nanotube structure and the carbon nanotube structure. The gap between adjacent carbon nanotubes and the ligaments of the porous metal structure.
請參閱圖3及圖4，該多孔金屬複合結構包括多孔金屬結構和一個奈米碳管結構，該奈米碳管結構固定在所述多孔金屬結構的表面，所述奈米碳管結構包括多根奈米碳管，所述多孔金屬複合結構包括多個褶皺部。Please refer to FIG. 3 and FIG. 4, the porous metal composite structure includes a porous metal structure and a nano carbon tube structure, and the nano carbon tube structure is fixed on the surface of the porous metal structure. A nano carbon tube, the porous metal composite structure includes a plurality of folds.
所述多孔金屬結構可以為多孔金屬膜、多孔金屬奈米片等任意結構。所述多孔金屬結構呈三維網狀，所述多孔金屬結構包括多個韌帶，該多個韌帶之間形成多個孔，所述多個孔可以呈規則分佈，如三維雙連續網路形式分佈，也可以呈不規則分佈。所述韌帶的材料為金、銀、鉑中的任意一種。該多個孔的孔徑為奈米級，優選的，所述多個孔的孔徑小於1000nm。The porous metal structure may be any structure such as a porous metal film, a porous metal nano sheet, and the like. The porous metal structure is a three-dimensional network, and the porous metal structure includes a plurality of ligaments. A plurality of holes are formed between the plurality of ligaments. The plurality of holes may be regularly distributed, such as a three-dimensional double continuous network. Can also be irregularly distributed. The material of the ligament is any one of gold, silver and platinum. The pore diameters of the plurality of pores are in the order of nanometers. Preferably, the pore diameters of the plurality of pores are less than 1000 nm.
所述奈米碳管結構可以通過一連接材料固定於所述多孔金屬結構表面。具體地，所述奈米碳管結構中的奈米碳管與所述多孔金屬結構中的韌帶接觸形成多個接觸面，該接觸面周圍設置有連接材料，使奈米碳管結構不容易脫離多孔金屬結構的表面。優選的，所述連接材料將所述接觸面包裹住。所述連接材料可以為有機粘結材料或金屬材料。所述有機粘結材料可以為萘酚等具有粘結作用的材料，所述金屬材料可以為Au、Ag、Cu等。優選的，所述金屬材料與所述多孔金屬結構的材料相同，減小金屬材料與多孔金屬結構中韌帶的接觸電阻。The nano carbon tube structure may be fixed on the surface of the porous metal structure through a connecting material. Specifically, the nano carbon tube in the nano carbon tube structure is in contact with the ligament in the porous metal structure to form a plurality of contact surfaces, and a connecting material is provided around the contact surface, so that the nano carbon tube structure is not easy to detach. Surface of porous metal structure. Preferably, the connection material covers the contact surface. The connection material may be an organic bonding material or a metal material. The organic bonding material may be a material having a bonding effect such as naphthol, and the metal material may be Au, Ag, Cu, or the like. Preferably, the metal material is the same as the material of the porous metal structure, and the contact resistance between the metal material and the ligament in the porous metal structure is reduced.
請參閱圖5及圖6，所述多個褶皺部100相互連接形成一連續結構。該褶皺部100由多孔金屬結構110和奈米碳管結構120共同彎折構成。這一點也可以從上述圖3中看出。在所述褶皺部100處，奈米碳管結構120的褶皺處的奈米碳管可以沿同一方向延伸。具體的，奈米碳管之間通過凡得瓦力首尾相連且沿同一方向排列。可以理解，奈米碳管結構的排列方向也可以不限。Please refer to FIGS. 5 and 6, the plurality of folds 100 are connected to each other to form a continuous structure. The corrugated portion 100 is formed by bending a porous metal structure 110 and a carbon nanotube structure 120 together. This can also be seen from the above-mentioned FIG. 3. At the fold portion 100, the nano carbon tubes at the folds of the nano carbon tube structure 120 may extend in the same direction. Specifically, the carbon nanotubes are connected end-to-end by Van der Waals and are aligned in the same direction. It can be understood that the arrangement direction of the carbon nanotube structure can also be unlimited.
所述褶皺部為不可逆轉的變形。由於奈米碳管具有良好的韌性，奈米碳管橫穿所述褶皺部，起到加固所述褶皺部的作用，奈米碳管結構與所述多孔金屬結構固定形成的多孔金屬複合結構具有良好的韌性，褶皺部不容易發生斷裂，該多孔金屬複合結構具備自支持的性能。The folds are deformed irreversibly. Because the nano carbon tube has good toughness, the nano carbon tube crosses the folds and plays a role of strengthening the folds. The porous metal composite structure formed by fixing the nano carbon tube structure and the porous metal structure has Good toughness, the folds are not easy to break, and the porous metal composite structure has self-supporting performance.
請參閱圖7，本發明實施例進一步提供一種多孔金屬複合結構的製備方法，其包括以下步驟:Referring to FIG. 7, an embodiment of the present invention further provides a method for preparing a porous metal composite structure, which includes the following steps:
步驟S20，提供一基板；Step S20, providing a substrate;
該基板的材料選擇受熱能夠收縮的材料。優選的，所述基板為塑膠板，該塑膠板的材料為聚苯乙烯、聚丙烯、聚對苯二甲醇乙二酯等。本實施例中，該塑膠板的材料為聚苯乙烯。The material of the substrate is selected from materials capable of shrinking when heated. Preferably, the substrate is a plastic plate, and the material of the plastic plate is polystyrene, polypropylene, polyethylene terephthalate, or the like. In this embodiment, the material of the plastic plate is polystyrene.
步驟S30，在所述基板的表面固定多孔金屬結構，形成第一複合結構；Step S30, fixing a porous metal structure on the surface of the substrate to form a first composite structure;
所述固定的方法不限，在某個實施例中，可以通過加熱所述基板，使基板稍微熔化從而粘住所述多孔金屬結構，優選的，將基板與多孔金屬結構在80°C的溫度下加熱30min～60 min；在另外一個實施例中，通過在所述基板與所述多孔金屬結構的接觸面周圍生長金屬，具體的，將所述第一複合結構轉移到含有Au+ 、Ag+ 、Cu+ 等任意一種金屬離子溶液中，在所述含有金屬離子的溶液中添加還原劑形成金屬顆粒，該金屬顆粒通過化學鍍的方式沉積在所述多孔金屬結構中韌帶與奈米碳管結構中奈米碳管的接觸處周圍，從而使多孔金屬結構固定在基板的表面。本實施例中，將基板與多孔金屬結構在80°C的溫度下加熱30min，加熱過程中所述基板的表面稍微發生熔融，多孔金屬結構粘合在所述基板的表面。The fixing method is not limited. In one embodiment, the substrate can be slightly melted by heating the substrate to stick to the porous metal structure. Preferably, the substrate and the porous metal structure are at a temperature of 80 ° C. Heating for 30 min to 60 min; in another embodiment, by growing metal around the contact surface between the substrate and the porous metal structure, specifically, transferring the first composite structure to a layer containing Au + , Ag + , In any metal ion solution such as Cu + , a reducing agent is added to the metal ion-containing solution to form metal particles, and the metal particles are deposited in the ligament and the carbon nanotube structure in the porous metal structure by electroless plating. The contact area of the nano carbon tube is around, so that the porous metal structure is fixed on the surface of the substrate. In this embodiment, the substrate and the porous metal structure are heated at a temperature of 80 ° C. for 30 minutes. During the heating process, the surface of the substrate is slightly melted, and the porous metal structure is adhered to the surface of the substrate.
所述多孔金屬結構的獲取方法不限，可以為目前市場上售賣的各種多孔金屬，也可以自行製備。本實施例中，所述多孔金屬結構為奈米多孔金膜，該奈米多孔金膜通過化學腐蝕的方法製備得到，具體方法如下：The method for obtaining the porous metal structure is not limited, and it can be various porous metals currently on the market, or it can be prepared by itself. In this embodiment, the porous metal structure is a nano porous gold film, and the nano porous gold film is prepared by a chemical etching method. The specific method is as follows:
S31，提供一Au-Ag合金薄膜。S31. Provide an Au-Ag alloy film.
該Au-Ag合金薄膜為表面光滑的薄膜材料，具有銀白色的光澤，其厚度範圍為50nm-200nm。該Au-Ag合金薄膜的尺寸不限，可以根據需要任意選擇。本實施例中，所述Au-Ag合金薄膜的厚度為100nm，該Au-Ag合金薄膜中所述金原子的百分比為35%，銀的原子百分比為65%。The Au-Ag alloy thin film is a thin film material with a smooth surface, and has a silver-white gloss, and the thickness ranges from 50 nm to 200 nm. The size of the Au-Ag alloy film is not limited, and can be arbitrarily selected according to needs. In this embodiment, the thickness of the Au-Ag alloy thin film is 100 nm, the percentage of the gold atoms in the Au-Ag alloy thin film is 35%, and the atomic percentage of silver is 65%.
S32，將所述Au-Ag合金薄膜放置於濃硝酸溶液中，直到該Au-Ag合金薄膜由銀白色變成棕紅色，形成奈米多孔金膜。S32. The Au-Ag alloy thin film is placed in a concentrated nitric acid solution until the Au-Ag alloy thin film changes from silver-white to brown-red to form a nano-porous gold film.
所述濃硝酸的濃度範圍可為50%-80%。通過玻璃片靜電吸附將該Au-Ag合金薄膜轉移到所述濃硝酸溶液中。本實施例中，所述濃硝酸的濃度為70%。所述Au-Ag合金中的Ag與濃硝酸進行反應，當Ag與濃硝酸反應完全後，所述Au-Ag合金薄膜變成棕紅色，此時，所述Au-Ag合金薄膜的表面形成多個不規則的孔，從而形成奈米多孔金膜。The concentration of the concentrated nitric acid may range from 50% to 80%. The Au-Ag alloy thin film was transferred into the concentrated nitric acid solution by electrostatic adsorption on a glass sheet. In this embodiment, the concentration of the concentrated nitric acid is 70%. The Ag in the Au-Ag alloy reacts with concentrated nitric acid. When the reaction between Ag and concentrated nitric acid is complete, the Au-Ag alloy film turns brown-red. At this time, a plurality of surfaces of the Au-Ag alloy film are formed. Irregular pores, thereby forming a nanoporous gold film.
請參閱圖8，所述奈米多孔金膜具有多個孔，多個孔之間通過韌帶連接，該多個孔的孔徑及韌帶尺寸與所述Au-Ag合金薄膜腐蝕的時間、濃硝酸濃度等因素有關。Please refer to FIG. 8, the nano porous gold film has multiple holes, and the multiple holes are connected by a ligament. The pore diameter and the ligament size of the multiple holes are related to the corrosion time and concentrated nitric acid concentration of the Au-Ag alloy film. And other factors.
S33，將所述奈米多孔金膜放置於去離子水中進行清洗。S33. The nano porous gold film is placed in deionized water for cleaning.
採用玻璃片將所述形成的奈米多孔金膜轉移到去離子水中浸泡清洗，在浸泡過程中不斷更換去離子水，使殘留在所述米多孔金膜韌帶上的硝酸徹底清洗掉。The formed nano porous gold film is transferred to deionized water for soaking and cleaning by using a glass sheet, and the deionized water is continuously replaced during the soaking process, so that the nitric acid remaining on the rice porous gold film ligament is thoroughly washed away.
步驟S40，在所述第一複合結構中多孔金屬結構的表面固定一個奈米碳管結構，形成第二複合結構；In step S40, a nano carbon tube structure is fixed on the surface of the porous metal structure in the first composite structure to form a second composite structure;
請參閱圖9及圖10，所述奈米碳管結構可以機械平鋪在所述多孔金屬結構的表面，該奈米碳管結構可以為線狀結構，如奈米碳管線，或可以為一奈米碳管膜狀結構。Referring to FIG. 9 and FIG. 10, the nano carbon tube structure may be mechanically tiled on the surface of the porous metal structure. The nano carbon tube structure may be a linear structure, such as a nano carbon pipeline, or may be a Nano carbon tube membrane structure.
所述奈米碳管線可以為一條或多條，當所述奈米碳管線為多條時，該多條奈米碳管線可以並排設置成束狀結構，也可以交叉設置成網狀結構，或者將該多條奈米碳管線相互扭轉形成一相互纏繞的絞線結構。The nano-carbon pipelines may be one or more. When the nano-carbon pipelines are multiple, the plurality of nano-carbon pipelines may be arranged side by side in a bundle structure, or may be arranged in a cross structure in a network structure, or The plurality of nano carbon pipelines are twisted with each other to form a twisted wire structure.
所述奈米碳管線可以為一非扭轉的奈米碳管線或扭轉的奈米碳管線。The nano carbon pipeline may be a non-twisted nano carbon pipeline or a twisted nano carbon pipeline.
該非扭轉的奈米碳管線包括多個沿該非扭轉的奈米碳管線長度方向排列的奈米碳管, 該多個奈米碳管基本相互平行，且該奈米碳管的軸向基本平行於該奈米碳管線的長度方向。具體地，該非扭轉的奈米碳管線中的沿非扭轉奈米碳管線軸向上的相鄰的奈米碳管通過凡得瓦力首尾相連。該非扭轉的奈米碳管線長度不限，直徑為0.5奈米~100微米。進一步地，該非扭轉的奈米碳管線可以用有機溶劑處理。The non-twisted nano carbon pipeline includes a plurality of nano carbon tubes arranged along a length direction of the non-twisted nano carbon pipeline, the plurality of nano carbon tubes are substantially parallel to each other, and an axial direction of the nano carbon tubes is substantially parallel to The length of the nano-carbon line. Specifically, among the non-twisted nano-carbon pipelines, adjacent nano-carbon pipes along the axial direction of the non-twisted nano-carbon pipelines are connected end-to-end by Van der Waals force. The non-twisted nanometer carbon pipeline has an unlimited length, with a diameter of 0.5 nanometers to 100 micrometers. Further, the non-twisted nano-carbon pipeline can be treated with an organic solvent.
所述扭轉的奈米碳管線包括多個繞該扭轉的奈米碳管線軸向螺旋排列的奈米碳管。該扭轉的奈米碳管線可採用一機械力將所述非扭轉的奈米碳管線兩端沿相反方向扭轉獲得。The twisted nanometer carbon pipeline includes a plurality of nanometer carbon tubes arranged in an axial spiral around the twisted nanometer carbon pipeline. The twisted nanometer carbon pipeline can be obtained by twisting two ends of the non-twisted nanometer carbon pipeline in opposite directions by using a mechanical force.
上述扭轉的奈米碳管線和非扭轉的奈米碳管線均由於其中的奈米碳管之間通過凡得瓦力緊密結合而使得該扭轉的奈米碳管線和非扭轉的奈米碳管線均具有自支撐結構。所述自支撐為奈米碳管線不需要大面積的載體支撐，而只要相對兩邊提供支撐力即能整體上懸空而保持自身線狀狀態，即將該奈米碳管線置於（或固定於）間隔一定距離設置的兩個支撐體上時，位於兩個支撐體之間的奈米碳管線能夠懸空保持自身線狀狀態。Both of the twisted nano carbon pipeline and the non-twisted nano carbon pipeline are tightly bonded by the van der Waals force between the nano carbon tubes, so that the twisted nano carbon pipeline and the non-twisted nano carbon pipeline are With self-supporting structure. The self-supporting nano-carbon pipeline does not require a large-area carrier support, and as long as the supporting forces are provided on the opposite sides, the whole can be suspended and maintained in a linear state, that is, the nano-carbon pipeline is placed (or fixed) at a space When the two support bodies are arranged at a certain distance, the nano carbon pipeline located between the two support bodies can be suspended to maintain its linear state.
所述奈米碳管膜狀結構可以為奈米碳管拉膜、奈米碳管絮化膜或奈米碳管碾壓膜中任意一種膜狀結。兩種以上膜狀結構的組合。當該奈米碳管膜狀結構為兩種以上膜狀結構，該兩種以上膜狀結構可以為共面設置或層疊設置，當該兩種以上膜狀結構層疊設置時，相鄰兩層奈米碳管膜狀結構中奈米碳管之間的夾角可以為0˚≦α≦90˚。The nano-carbon tube film-like structure may be any one of a nano-carbon tube drawn film, a nano-carbon tube flocculated film, or a nano-carbon tube laminated film. A combination of two or more film-like structures. When the nanometer carbon tube film structure is two or more film structures, the two or more film structures may be coplanar or stacked. When the two or more film structures are stacked, two adjacent layers The angle between the carbon nanotubes of the carbon nanotube film structure can be 0˚ ≦ α ≦ 90 ≦.
所述奈米碳管拉膜可以為一層或多層，當奈米碳管拉膜為多層時，該多層奈米碳管拉膜可以為共面設置或層疊設置。本實施例中，所述奈米碳管結構為奈米碳管拉膜，由於該奈米碳管拉膜中的奈米碳管通過凡得瓦力首尾相連且沿同一方向延伸，能夠減小所述多孔金屬複合結構的內部阻抗，提高其導電性。The nano-carbon tube drawn film may be one or more layers. When the nano-carbon tube drawn film is multiple layers, the multi-layered carbon nanotube drawn film may be coplanar or stacked. In this embodiment, the nano carbon tube structure is a nano carbon tube drawing film. Since the nano carbon tubes in the nano carbon tube drawing film are connected end to end by Van der Waals and extend in the same direction, it can be reduced. The internal impedance of the porous metal composite structure improves its conductivity.
所述奈米碳管拉膜為由若干奈米碳管組成的自支撐結構。所述若干奈米碳管基本沿同一方向擇優取向排列，所述擇優取向排列是指在奈米碳管拉膜中大多數奈米碳管的整體延伸方向基本朝同一方向。而且，所述大多數奈米碳管的整體延伸方向基本平行于奈米碳管拉膜的表面。進一步地，所述奈米碳管拉膜中大多數奈米碳管是通過凡得瓦力首尾相連。具體地，所述奈米碳管拉膜中基本朝同一方向延伸的大多數奈米碳管中每一奈米碳管與在延伸方向上相鄰的奈米碳管通過凡得瓦力首尾相連。當然，所述奈米碳管拉膜中存在少數隨機排列的奈米碳管，這些奈米碳管不會對奈米碳管拉膜中大多數奈米碳管的整體取向排列構成明顯影響。The nano-carbon tube drawn film is a self-supporting structure composed of several nano-carbon tubes. The plurality of carbon nanotubes are arranged in a preferred orientation along substantially the same direction. The preferred orientation refers to that the overall extending direction of most of the carbon nanotubes in the film of the carbon nanotube is substantially the same. Moreover, the overall extending direction of most of the carbon nanotubes is substantially parallel to the surface of the carbon nanotube drawn film. Further, most of the nano carbon tubes in the nano carbon tube pulling film are connected end-to-end by Van der Waals force. Specifically, each of the nano-carbon tubes in the nano-carbon tube drawn film extending substantially in the same direction is connected end-to-end with a van der Waals force by adjacent carbon nanotubes in the extending direction. . Of course, there are a few randomly arranged carbon nanotubes in the carbon nanotube drawn film, and these carbon nanotubes will not significantly affect the overall alignment of most of the carbon nanotubes in the carbon nanotube drawn film.
所述奈米碳管碾壓膜可以為一層或多層，當奈米碳管碾壓膜為多層時，該多層奈米碳管碾壓膜可以為共面設置或層疊設置。The nano carbon tube rolled film may be one or more layers. When the nano carbon tube rolled film is multi-layer, the multi-layered nano carbon tube rolled film may be coplanar or stacked.
所述奈米碳管碾壓膜包括均勻分佈的奈米碳管，該奈米碳管無序，沿同一方向或不同方向擇優取向排列。優選地，所述奈米碳管碾壓膜中的奈米碳管基本沿同一方向延伸且平行於該奈米碳管碾壓膜的表面。所述奈米碳管碾壓膜中的奈米碳管相互交疊，從而使所述奈米碳管碾壓膜的表面較為粗糙。所述奈米碳管碾壓膜中奈米碳管之間通過凡得瓦力相互吸引並形成多個間隙。該奈米碳管碾壓膜具有很好的柔韌性，可以彎曲折疊成任意形狀而不破裂。所述奈米碳管絮化膜可以為一層或多層，當奈米碳管絮化膜為多層時，該多層奈米碳管絮化膜可以為共面設置或層疊設置。The nano carbon tube rolling film includes uniformly distributed nano carbon tubes, the nano carbon tubes are disordered, and are arranged in a preferred orientation in the same direction or different directions. Preferably, the nano carbon tube in the nano carbon tube rolled film extends substantially in the same direction and is parallel to the surface of the nano carbon tube rolled film. The nano carbon tubes in the nano carbon tube rolling film overlap each other, so that the surface of the nano carbon tube rolling film is rough. Nano carbon tubes in the nano carbon tube rolling film are attracted to each other by van der Waals force and form a plurality of gaps. The nano carbon tube rolled film has good flexibility and can be bent and folded into any shape without breaking. The nano carbon tube flocculation film may be one or more layers. When the nano carbon tube flocculation film is multi-layer, the multi-layer nano carbon tube flocculation film may be coplanar or stacked.
所述奈米碳管絮化膜包括相互纏繞的奈米碳管。該奈米碳管之間通過凡得瓦力相互吸引、纏繞形成網狀結構，從而使所述奈米碳管絮化膜的表面較為粗糙。所述奈米碳管絮化膜中的奈米碳管為均勻分佈，無規則排列。The nano carbon tube flocculating film includes nano carbon tubes intertwined with each other. The nano carbon tubes are attracted and entangled with each other by Van der Waals force to form a network structure, so that the surface of the nano carbon tube flocculating film is rough. The nano carbon tubes in the nano carbon tube flocculation film are uniformly distributed and arranged irregularly.
所述固定奈米碳管結構的方法有兩種：（一）通過有機粘結材料來固定：在所述第一複合結構中奈米碳管結構的表面滴加有機粘結材料，該有機粘結材料通過所述奈米碳管中的間隙進入所述多孔金屬結構，該有機粘結材料將所述多孔金屬結構和奈米碳管結構的接觸面包裹住；（二）通過金屬材料固定：將所述第二複合結構轉移到含有Au+ 、Ag+ 、Cu+ 等任意一種金屬離子溶液中，在所述含有金屬離子的溶液中添加還原劑形成金屬顆粒，該金屬顆粒通過化學鍍的方式沉積在所述多孔金屬結構中韌帶與奈米碳管結構中奈米碳管的接觸處周圍，從而使多孔金屬結構和奈米碳管結構結合在一起。本實施例中，將第一複合結構轉移到含有Au+ 溶液中，採用水合肼對Au+ 進行還原生成Au，生成的Au包裹所述韌帶與奈米碳管的接觸面周圍。There are two methods for fixing the carbon nanotube structure: (1) Fixing by an organic bonding material: an organic bonding material is dripped on the surface of the carbon nanotube structure in the first composite structure, and the organic bonding The junction material enters the porous metal structure through the gap in the nano carbon tube, and the organic bonding material wraps the contact surface of the porous metal structure and the nano carbon tube structure; (2) fixed by the metal material: The second composite structure is transferred to a solution containing any one of metal ions such as Au + , Ag + , Cu +, etc., and a reducing agent is added to the solution containing metal ions to form metal particles. The metal particles are formed by electroless plating. It is deposited around the contact between the ligament in the porous metal structure and the nano carbon tube in the nano carbon tube structure, thereby combining the porous metal structure and the nano carbon tube structure together. In this embodiment, the first composite structure is transferred to a solution containing Au + , and Au + is reduced by using hydrazine hydrate to generate Au, and the generated Au wraps around the contact surface of the ligament and the carbon nanotube.
步驟S50，使所述第二複合結構發生皺縮，形成一多孔金屬複合結構。In step S50, the second composite structure is shrunk to form a porous metal composite structure.
該第二複合結構發生皺縮的方法不限，只要能夠使所述基板、多孔金屬結構及奈米碳管結構形成的第二複合結構發生褶皺即可。本實施例中，將所述第二複合結構在160°C的溫度下加熱2min，該基板發生皺縮，由於所述多孔金屬結構固定在所述基板表面，奈米碳管結構固定在所述多孔金屬結構表面，因此所述基板發生皺縮的過程中會帶動所述多孔金屬結構與所述奈米碳管膜一起發生皺縮，此時所述多孔金屬結構不容易斷裂，形成的多孔複合結構具有良好的韌性。The method for generating the second composite structure to be shrunk is not limited, as long as the second composite structure formed by the substrate, the porous metal structure, and the carbon nanotube structure can be wrinkled. In this embodiment, the second composite structure is heated at a temperature of 160 ° C for 2 minutes, and the substrate is shrunk. Since the porous metal structure is fixed on the surface of the substrate, the nano carbon tube structure is fixed on the substrate. The surface of the porous metal structure, so the process of shrinking the substrate will cause the porous metal structure to shrink together with the carbon nanotube film. At this time, the porous metal structure is not easily broken, and a porous composite is formed. The structure has good toughness.
本發明實施例提供的多孔金屬複合結構及其製備方法具有以下優點：其一，奈米碳管具有良好的韌性，提高了多孔金屬複合結構的韌性，使多孔金屬複合結構不容易發生脆斷；其二，由於奈米碳管具有良好的導電性，從而提高了多孔金屬複合結構的導電性。The porous metal composite structure and the preparation method thereof provided by the embodiments of the present invention have the following advantages: first, the nano carbon tube has good toughness, improves the toughness of the porous metal composite structure, and makes the porous metal composite structure less prone to brittle fracture; Secondly, because the carbon nanotubes have good conductivity, the conductivity of the porous metal composite structure is improved.
本發明進一步提供一種生物感測器，該生物感測器包括一分子識別元件和一訊號轉換元件，該訊號轉換元件將所述分子識別元件識別到的生化反應訊號轉換成電化學訊號，所述分子識別元件包括一多孔金屬複合結構，該多孔金屬複合結構包括一多孔金屬結構及一奈米碳管結構，該奈米碳管結構固定在所述多孔金屬結構的表面，所述奈米碳管結構包括多根奈米碳管，所述多孔金屬複合結構包括多個褶皺部。The present invention further provides a biosensor. The biosensor includes a molecular recognition element and a signal conversion element. The signal conversion element converts a biochemical reaction signal identified by the molecular recognition element into an electrochemical signal. The molecular recognition element includes a porous metal composite structure including a porous metal structure and a nano carbon tube structure, and the nano carbon tube structure is fixed on the surface of the porous metal structure. The carbon tube structure includes a plurality of nano carbon tubes, and the porous metal composite structure includes a plurality of folds.
所述多孔金屬複合結構與所述待測生物分子發生反應，該分子識別元件用於識別待測生物分子被催化後產生的生化反應訊號，該分子識別元件中的催化劑與所述待測生物分子發生反應。所述待測生物分子可以為葡萄糖分子、有機分子、酶、酶的底物、抗體或抗原等。本實施例中，待測生物分子為葡萄糖。The porous metal composite structure reacts with the biomolecule to be tested. The molecular recognition element is used to identify a biochemical reaction signal generated after the biomolecule to be tested is catalyzed. The catalyst in the molecular recognition element and the biomolecule to be tested react. The biomolecule to be detected may be a glucose molecule, an organic molecule, an enzyme, an enzyme substrate, an antibody, an antigen, or the like. In this embodiment, the biomolecule to be measured is glucose.
所述多孔金屬複合結構與所述待測生物分子接觸，該待測生物分子在一定的電壓下被催化產生生化反應訊號，所述訊號轉換元件將該生化反應訊號轉換成實體訊號並輸出到一訊號處理系統，通過處理該實體訊號從而對所述待測生物分子的濃度進行監測。所述多孔金屬複合結構中多孔金屬結構與奈米碳管結構均具有良好的催化性能，且由於多孔金屬結構與奈米碳管結構均具有良好的導電性，因此，所述多孔金屬複合材料可同時用於收集電子和催化，結構簡單，減小了分子識別元件的內部電阻。The porous metal composite structure is in contact with the biomolecule to be tested. The biomolecule to be tested is catalyzed to generate a biochemical reaction signal under a certain voltage. The signal conversion element converts the biochemical reaction signal into a physical signal and outputs it to The signal processing system monitors the concentration of the biomolecule to be measured by processing the physical signal. Both the porous metal structure and the nano carbon tube structure in the porous metal composite structure have good catalytic performance, and since the porous metal structure and the nano carbon tube structure both have good conductivity, the porous metal composite material can be Simultaneously used for collecting electrons and catalysis, the structure is simple, and the internal resistance of the molecular recognition element is reduced.
所述分子識別元件可進一步包括催化材料，該催化材料設置於所述多孔金屬複合結構的表面，該催化材料可以為金屬氧化物、金屬等，能夠進一步提高所述分子識別元件的催化性能。所述奈米氧化物可以通過化學或電化學的方法生長在所述多孔金屬複合結構的表面。所述金屬氧化物可以為Co3 O4 、MnO2 等材料，所述金屬氧化物的形狀可以為奈米顆粒、奈米片、奈米花等。The molecular recognition element may further include a catalytic material disposed on a surface of the porous metal composite structure, and the catalytic material may be a metal oxide, a metal, or the like, which can further improve the catalytic performance of the molecular recognition element. The nano-oxide can be grown on the surface of the porous metal composite structure by chemical or electrochemical methods. The metal oxide may be materials such as Co 3 O 4 and MnO 2, and the shape of the metal oxide may be nano particles, nano flakes, nano flowers, and the like.
所述訊號轉換元件可以為物理或化學換能器，該換能器可以為氧電極、光敏管、場效應管、壓電晶體等中的任意一種，該訊號轉換元件將所述分子識別元件識別到的生化反應訊號轉換成可測量的電化學訊號，從而得到待測生物分子的濃度。The signal conversion element may be a physical or chemical transducer. The transducer may be any one of an oxygen electrode, a photosensitive tube, a field effect tube, a piezoelectric crystal, and the like. The signal conversion element recognizes the molecular recognition element. The obtained biochemical reaction signal is converted into a measurable electrochemical signal, thereby obtaining the concentration of the biomolecule to be measured.
本發明實施例提供的生物感測器電極及生物感測器具有如下優點：其一，奈米碳管結構固定於多孔金屬結構的表面，多孔金屬複合結構具有良好的機械強度、韌性和導電性，提高了生物感測器電極及生物感測器的韌性、機械強度和導電性，延長了生物感測器電極及生物感測器的使用壽命；其二，所述多孔金屬結構和奈米碳管結構均具有良好的催化性能，所述生物感測器電極可同時收集電子和進行催化，無需額外引入催化材料，結構簡單、方便；其三，在所述多孔金屬複合結構表面形成催化材料，降低了生物感測器電極的內阻，進一步提高了生物感測器電極及生物感測器的導電性。The biosensor electrode and biosensor provided by the embodiments of the present invention have the following advantages: First, the carbon nanotube structure is fixed on the surface of the porous metal structure, and the porous metal composite structure has good mechanical strength, toughness and conductivity. , Improves the toughness, mechanical strength and conductivity of the biosensor electrode and biosensor, and prolongs the service life of the biosensor electrode and biosensor; second, the porous metal structure and nano carbon The tube structures all have good catalytic performance. The biosensor electrodes can collect electrons and perform catalysis at the same time, without the need to introduce additional catalytic materials, and the structure is simple and convenient. Third, a catalytic material is formed on the surface of the porous metal composite structure. The internal resistance of the biosensor electrode is reduced, and the conductivity of the biosensor electrode and the biosensor is further improved.
綜上所述，本發明確已符合發明專利之要件，遂依法提出專利申請。惟，以上所述者僅為本發明之較佳實施例，自不能以此限制本案之申請專利範圍。舉凡習知本案技藝之人士援依本發明之精神所作之等效修飾或變化，皆應涵蓋於以下申請專利範圍內。In summary, the present invention has indeed met the requirements for an invention patent, and a patent application was filed in accordance with the law. However, the above is only a preferred embodiment of the present invention, and it cannot be used to limit the scope of patent application in this case. Any equivalent modification or change made by those who are familiar with the skills of this case with the aid of the spirit of the present invention shall be covered by the scope of the following patent applications.
無no
圖1是先前技術中褶皺的奈米多孔金膜在高倍下的掃描電鏡圖。FIG. 1 is a scanning electron microscope image of a folded nano-porous gold film at a high magnification in the prior art.
圖2是本發明實施例提供的形成有MnO2 的多孔金屬複合結構在高倍鏡下的掃描電鏡圖。FIG. 2 is a scanning electron microscope image of a porous metal composite structure formed with MnO 2 according to an embodiment of the present invention under a high power microscope.
圖3是本發明實施例提供的多孔金屬複合結構在低倍鏡下的掃描電鏡圖。FIG. 3 is a scanning electron microscope image of a porous metal composite structure provided by an embodiment of the present invention under a low magnification mirror.
圖4是本發明實施例提供的多孔金屬複合結構在高倍鏡下的掃描電鏡圖。FIG. 4 is a scanning electron microscope image of a porous metal composite structure provided by an embodiment of the present invention under a high power microscope.
圖5是本發明實施例提供的多孔金屬複合結構的掃描電鏡圖。FIG. 5 is a scanning electron microscope image of a porous metal composite structure provided by an embodiment of the present invention.
圖6是本發明實施例圖5中褶皺部的結構示意圖。FIG. 6 is a schematic structural diagram of a fold portion in FIG. 5 according to an embodiment of the present invention.
圖7是本發明實施例提供的多孔金屬複合結構製備方法的流程示意圖。FIG. 7 is a schematic flowchart of a method for preparing a porous metal composite structure according to an embodiment of the present invention.
圖8是本發明實施例提供的多孔金屬複合結構中奈米多孔金膜的掃描電鏡表徵圖。FIG. 8 is a scanning electron microscope characteristic diagram of a nano-porous gold film in a porous metal composite structure provided by an embodiment of the present invention.
圖9是本發明實施例提供的多孔金屬複合結構中第二複合結構的掃描電鏡表徵圖。FIG. 9 is a scanning electron microscope characterization diagram of a second composite structure in a porous metal composite structure provided by an embodiment of the present invention.
圖10是本發明實施例提供的多孔金屬複合結構中第二複合結構的掃描電鏡圖。FIG. 10 is a scanning electron microscope image of a second composite structure in a porous metal composite structure provided by an embodiment of the present invention.
無no
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